Thermotropic liquid–crystalline properties of 4,4′-dialkoxy-3,3′-diaminobiphenyl compounds and their precursors

A series of 4,4?-dialkoxy-3,3?-diaminobiphenyl compounds were synthesised by three-step procedure that involves alkylation, nitration and reduction reactions. Their chemical structures were characterised by FTIR, ¹H and ¹³C spectroscopy and elemental analysis. Their thermotropic liquid–crystalline (LC) properties were examined by a number of experimental techniques including differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarising optical microscopy (POM) and variable temperature X-ray diffraction (VT-XRD). The 4,4?-dialkoxy-3,3?-dinitrobipheyl compounds, precursors to the diamine compounds, were also examined for their thermotropic LC properties. POM studies of focal conic textures and VT-XRD of the 3,3?-diaminobiphenyl derivatives having flexible alkyl chains (C₆–C₁₂) exhibited the smectic A (SmA) phase independent of the length of alkyl chains. Similarly, the 3,3?-dinitrobiphenyl derivatives containing alkyl chains C₇, and C₉–C₁₁ exhibit the SmA phase, those containing C₈ formed the smectic C (SmC) phase and C₁₂ formed both the SmA and smectic B (SmB) phases, respectively. The 3,3?-diaminobiphenyl derivatives had excellent thermal stability in the temperature range of 237–329°C, while those of 3,3?-dinitrobiphenyl derivatives were in the temperature range of 270–321°C. The 3,3?-diaminobiphenyl derivatives emitted UV light both in chloroform and acetonitrile.     

Effect of counter-ion on the thermotropic liquid crystal behaviour of bis(alkyl)-tris(imidazolium salt) compounds

Recently, new thermotropic ionic liquid crystals (LCs) with a hexyl-linked tris(imidazolium bromide) core and two terminal alkyl chains were synthesised and characterised. To explore the effect of different counter-ions on the LC behaviour of this system, derivatives with BF₄^? and Tf₂N^? counter-ions were prepared and analysed. Five of the BF₄^? derivatives were found to exhibit thermotropic LC behaviour. The 12-, 14- and 16-carbon tail BF₄^? compounds form SmA phases. The 18- and 20-carbon tail homologues form what appears to be a smectic phase but are weakly mesogenic and harder to characterise. Only two of the Tf₂N^? derivatives exhibited mesogenic behaviour. The 18-carbon tail Tf₂N^? compound forms an as-yet unidentified, highly periodic smectic phase with positional order while the 20-carbon tail homologue forms a periodic SmA phase. The Tf₂N^? mesogens have much lower clearing points even though their LC phases have more order than the Br^? and BF₄^? mesogens. X-ray diffraction showed that these mesogens have different amounts of tail interdigitation between the smectic layers depending on the counter-ion present. Atomistic molecular dynamics simulations indicated that counter-ion size plays an important role in defining the density of the ionic region, which in turn affects the amount of interdigitation in the smectic phases.     

Thermotropic liquid crystal behaviour of gemini imidazolium-based ionic amphiphiles

Thermotropic ionic liquid crystals (LCs) are useful for a number of applications such as anisotropic ion transport and as organised reaction media/solvents because of their ordered fluid properties and intrinsic charge units. A large number of different ionic LC architectures are known, but only a handful of examples of gemini (i.e. paired or dimeric) ionic LCs have been prepared and studied. In this work, a series of 20 new symmetric, imidazolium-based, gemini cationic LCs containing two bridged imidazolium cations and two pendant alkyl chains was synthesised, and the thermotropic LC behaviours were characterised. The imidazolium unit provides a highly tunable and modular platform for the design and synthesis of gemini cationic LCs which offers excellent structure control. As expected, the thermotropic LC properties of these new amphilphilic, gemini ionic LCs were found to be strongly influenced by the length of the spacer between the imidazolium units, the length of the pendant alkyl tails, and the nature of the anion. Smectic A (SmA) thermotropic LC phases were observed in more than half of the gemini imidazolium LC systems studied.     

Investigations on liquid crystalline partially fluorinated alkyl and succinimidyl benzoates

The synthesis and mesophase properties of partially fluorinated alkoxy‐substituted benzoic alkyl and succinimidyl (NHS) esters with one, two and three perfluoroalkyl alkoxy chains are reported. The mesophases were studied using differential scanning calorimetry (DSC), polarizing optical microscopy and X‐ray diffraction of non‐oriented samples. The SmA phases of the one‐chain methyl esters are monotropic, while those of the one‐chain NHS esters are enantiotropic. The more wedge‐shaped two‐ and three‐chain alkyl esters do not form mesophases, whereas the succinimidyl analogues exhibit hexagonal columnar phases. Their enhanced mesophase stability is caused by the higher polarity of the succinimidyl ring with respect to the alkyl ester groups. Aggregation of the dipolar succinimidyl groups, together with the microsegregation of the lipophilic and fluorophilic segments of the partially fluorinated alkoxy chains, is assumed to lead to a threefold structured morphology in both the SmA and the Col_h phases. This threefold structuring can be regarded as analogous to known morphologies of ABC triblock copolymers.     

Bromine-terminated azobenzene liquid crystals

A series of liquid crystals (LCs) of bromine-terminated azobenzene were synthesised and characterised. The LCs were composed of an azobenzene core, an alkyl chain and a flexible spacer with a bromine atom at a remote position. Mesomorphic properties were dependent on both the alkyl chain length and the relative position of the bromine atom at the end of the spacer group. The nematic phase was favoured over the smectic A phase for alkyl chains with one and seven carbon atoms. However, the SmA mesophase was dominant for compounds with 10-carbon alkyl chains. The remote bromine atom in the spacer group favoured SmA for homologous with n-decyl chains and the nematic phase for n-heptyl and methyl groups. Molecular modelling showed that the azobenzene LCs tended to adopt the all trans-conformation in the gas phase as the number of carbon atoms increased. For short spacer groups, bent conformations contributed to the level population proportion of conformers. For the non-LC 5a, the gauche conformation became the most stable with a torsional angle of –68.9°. X-ray experiments showed a monolamellar SmA mesophase in an antiparallel arrangement. Absorption maxima at 360 and 440 nm were assigned to π–π* and n–π* transitions, respectively.     

Synthesis and liquid crystalline investigation of chiral 6-alkoxy-2-naphathoic acid derivatives

A two new series of materials with a chiral fragment derived from ((S)-(─)-2-methyl-1-butanol and 6-alkoxy-2-naphathoic acid as the molecular core was synthesised and investigated. All the homologues exhibited enantiotropic mesomorphism. Chiral smectic C (SmC*), smectic A (SmA) and chiral nematic (N*) phases were observed in different homologues. All the compounds were characterised by spectroscopic and elemental analysis. Thermal investigations and mesophase characterisations for all the compounds were carried out by the combination of DSC and POM analysis. The effects of the central linkage and various terminal normal alkyl chains with its structurally related compounds have been discussed.     

Self‐Assembly of Imidazolium‐Based Rodlike Ionic Liquid Crystals: Transition from Lamellar to Micellar Organization

By using aryl‐amination chemistry, a series of rodlike 1‐phenyl‐1H‐imidazole‐based liquid crystals (LCs) and related imidazolium‐based ionic liquid crystals (ILCs) has been prepared. The number and length of the C‐terminal chains (at the noncharged end of the rodlike core) and the length of the N‐terminal chain (on the imidazolium unit in the ILCs) were modified and the influence of these structural parameters on the mode of self‐assembly in LC phases was investigated by polarizing microscopy, differential scanning calorimetry, and X‐ray diffraction. For the single‐chain imidazole derivatives nematic phases (N) and bilayer SmA₂ phases were found, but upon increasing the number of alkyl chains the LC phases were lost. For the related imidazolium salts LC phases were preserved upon increasing the number and length of the C‐terminal chains and in this series it leads to the phase sequence SmA–columnar (Col)–micellar cubic (Cub_I/Pm3n). Elongation of the N‐terminal chain gives the reversed sequence. Short N‐terminal chains prefer an end‐to‐end packing of the mesogens in which these chains are separated from the C‐terminal chains. Elongation of the N‐terminal chain leads to a mixing of N‐ and C‐terminal chains, which is accompanied by complete intercalation of the aromatic cores. In the smectic phases this gives rise to a transition from bilayer (SmA₂) to monolayer smectic (SmA) phases. For the columnar and cubic phases the segregated end‐to‐end packing leads to core–shell aggregates. In this case, elongation of the N‐terminal chains distorts core–shell formation and removes Cub_I and Col phases in favor of single‐layer SmA phases. Hence, by tailoring the length of the N‐terminal chain, a crossover from taper‐shaped to polycatenar LC tectons was achieved, which provides a powerful tool for control of self‐assembly in ILCs.     

New side chain cholesterol-functionalised aliphatic polycarbonate copolymer: synthesis and phase behaviour

A new side cholesterol-functionalised liquid crystal (LC) copolymer based on aliphatic polycarbonate backbone was synthesised. The chemical structures of the block copolymers obtained in this study were characterised with Fourier Transform Infrared Spectroscopy (FT-IR) and Proton Nuclear Magnetic Resonance (¹H NMR) spectra. Their thermal stability and phase behaviours were investigated with thermogravimetric analysis (TGA) measurements, differential scanning calorimetry, and polarising optical microscopy. The molecular organisation in the mesophase was studied by temperature-dependent X-ray diffraction (XRD). As a result, the block copolymer bearing side cholesteryl groups showed a glass transition at 15.8°C and a smectic A (SmA) to isotropic phase transition at 151.3°C on heating cycle. XRD indicated that the block LC copolymer showed an interdigitated molecular arrangement of the mesogenic units within the smectic layers. This partial bilayer structure was similar to the SmA phase formed by polar mesogens.     

Synthesis and characterisation of some new chalcone liquid crystals

A series of new chalcones with four aromatic rings is synthesised and characterised. The chemical structures of chalcones are evaluated by Fourier transform-infrared spectroscopy, elemental analysis, ¹H and ¹³C nuclear magnetic resonance spectroscopic techniques. The compounds were investigated for liquid crystalline properties using differential scanning calorimetry and polarising optical microscopy with hot stage. The results indicate that the formation of mesophase type is dependent on the alkyl chain length at one end of the molecule. Compounds 9a–d with relatively shorter chains show SmA and nematic mesophases, whereas 9e–g exhibit SmC and SmA mesophases. Compound 9h having a cyano group at one end, exhibit SmA and nematic mesophases.     

Alkyl chain self ordering,induction and suppression of mesophase by Cu(II) containing [1,2,3]-triazole-based bidentate salicylaldimine ligands: synthesis,characterisation and X-ray diffraction studies

Some new Cu(II) complexes containing [1,2,3]-triazole-based bidentate salicylaldimine and its analogues with terminal substituent (F, Cl, Br and I) have been synthesieed. All the target complexes and their uncoordinated ligands were elucidated by elemental analysis and spectroscopic techniques (UV-visible, FT-IR, 1D, 2D ¹H and ¹³C-NMR). The polarising optical microscope and differential scanning calorimetry (DSC) have disclosed all complexes and ligands are mesomorphic except the complex without any terminal substituent. The fluoro-substituted complexes with even parity C₁₄H₂₉ and C₁₆H₃₃ exhibit new enantiotropic nematic phase which was absent in their corresponding ligands, whereas the suppression of SmC phase occurred for all complexes with longer C₁₆H₃₃ and C₁₈H₃₇. X-ray diffraction confirmed the existence of SmA, SmC and N phases for complexes and ligands. The other notable feature is that the self-ordering of terminal alkyl chain occurred in SmA and SmC phases of complexes with even terminal alkyl chain ranging from C₁₄H₂₉ to C₁₈H₃₃. Their corresponding ligands exhibit intercalated structure of SmA and SmC phases. The thermal behaviour studies show that the fluoro-substituted triazole-based complexes possess lowest phase transition temperature and more stable as compared to other substituent which decomposed during the isotropisation.     

Synthesis and characterisation of novel isoxazole-based banana liquid crystals from naturally occurring curcumin

Isoxazole-based bent-core liquid crystals (LCs) derived from naturally occurring curcumin were synthesised and their LC properties were investigated by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction techniques. Five compounds, including a branched alkyl chain derivative, were prepared and characterised. These derivatives exhibit enantiotropic mesophases. While lower homologues display wide-temperature-range nematic phase, a longer-chain derivative 3d shows smectic C phase in addition to the nematic phase. The bent angle in these compounds is in between calamitic LCs and banana LCs. Therefore, the molecules escape from polar order packing observed in typical bent-core LCs. Increasing the length of alkyl chain reduces both melting and isotropic temperatures in the series. However, the compound with branched alkyl chains exhibits significant reduction in the nematic-isotropic temperature only. Detailed XRD experiments confirm the presence of the N phase in the lower homologues and SmC phase in a higher homologue.     

Amphiphilic taper-shaped oligomer exhibiting a monolayer smectic A to columnar phase transition

We prepared two series of liquid-crystalline oligomers composed of phenylpyrimidine based mesogenic cores, alkyl spacers and semiperfluorinated alkyl chains in one series and only alkyl chains in the second series. Their physical properties were investigated using optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. The oligomers possessing a semiperfluorinated alkyl chain show a phase sequence of SmC–SmA–Col when the number of phenylpyrimidine moieties was increased. The compound possessing three phenylpyrimidine cores was found to exhibit monolayer SmA and Col phases. On the other hand, the oligomer composed of an alkyl chain and three phenylpyrimidine cores showed only a nematic phase. We discuss effects of the shape amphiphilicity and the hydrocarbon–fluorocarbon amphiphilicity on phase transition behaviour of the amphiphilic oligomers.     

Synthesis and studies of some 4-substituted phenyl-4′-azopyridine-containing hydrogen-bonded supramolecular mesogens

Novel azopyridine-containing supramolecular liquid crystalline (LC) materials built via 1 : 1-heterointermolecular hydrogen bonding between some 4-substituted phenyl-4′-azopyridines and 4-n-alkyloxybenzoic acids are reported. These hydrogen-bonded LC complexes exhibit well defined nematic, smectic A and smectic C phases over wide ranges of temperature depending upon the number of carbon atoms present in the alkyl chains. The formation of pure LC materials on 1 : 1-complexation could be confirmed from the phase diagrams of the binary mixtures, which clearly indicated a melting maximum for the 50 mol% mixture as well as the presence of two eutectic points on either side of this mixture.     

Ionic Complexes of Polyacids and Cationic Surfactants

Comb-like ionic complexes were prepared from polyuronic acids (pectinic and alginic acids) and alkyltrimethylammonium surfactants bearing linear alkyl chains with 18, 20 and 22 carbon atoms. In the condensed state, these complexes were able to self-assemble in ordered structures which were thermally stable up to ∼200 °C. The complexes were analysed by DSC and WAXS/SAXS and compared to their analogous made from poly(γ-glutamic acid). They all adopt a biphasic layered structure in which the main chain and the alkyl side chain alternate with a nanometric periodicity. Alkyl side chains were partially crystallized in these complexes and they show reversible melting at temperatures within the 60-80 °C range depending on the length of the polymethylene segment.     

Peripheral chain length-dependent complex phase behaviour in C3-symmetric hexa-alkylated liquid crystals

We report the thermal and self-assembly properties of C₃-symmetric liquid crystalline (LC) molecules consisting of a conformationally tunable triazole-based mesogen and six-fold alkyl chains. Unlike the LC compound (1) based on non-crystallisable octyl chains, 2 and 3, which have crystallisable dodecyl and tetradecyl chains, respectively, exhibit a cold crystallisation which only takes place under slow heating conditions (2°C/min). In contrast with the vertically interdigitated lamellar crystalline phase of 1, a laterally interdigitated bilayered lamellar structure driven by the crystallisation of the dodecyl or tetradecyl chains is observed in the cold crystallisation temperature range. In addition to their crystalline morphology, 2 and 3 show LC morphological behaviour distinct from that of 1, 2 and 3 exhibit a hexagonal columnar LC phase consisting of T-shaped conformers rather than the lamellar LC phase of 1. The morphological transformation from the lamellar (1) to the columnar phase (2 and 3) can be rationalised by the alleviation of the conformational energy of the longer alkyl chains. Consequently, the simple variation of alkyl chain length in the C₃-symmetric LC system results in contrasting thermal and assembly properties in the crystalline and LC phases.     

Main‐chain viologen polymers with organic counterions exhibiting thermotropic liquid‐crystalline and fluorescent properties*

A series of viologen polymers with bromide, tosylate, and triflimide as counterions were prepared by either the Menshutkin reaction or metathesis reaction in a common organic solvent. Their polyelectrolyte behavior in methanol was determined by solution viscosity measurements, and their chemical structures were determined by Fourier transform infrared and Fourier transform NMR spectroscopy. They were characterized for their thermotropic liquid‐crystalline properties with a number of experimental techniques. Each of the viologen polymers with organic counterions had a low melting transition or fusion temperature above which it formed either a high‐order smectic phase or a low‐order smectic phase. Each of them also exhibited a smectic‐to‐isotropic transition. The ranges of the liquid‐crystalline phase were 80–88 °C for viologen polymers with tosylate as a counterion and 120–146 °C for viologen polymers with triflimide as a counterion. They had excellent thermal stability. The ranges of thermal stability were 288–329 °C for viologen polymers with tosylate as a counterion and 343–350 °C for viologen polymers with triflimide as a counterion. The fluorescence property for all of the viologen polymers in either aqueous or methanol solution was also included in this study. For example, the viologen polymer containing the 4,4′‐bipyridinium and p‐xylyl units along the backbone of the polymer chain with triflimide as a counterion had an absorption spectrum (λ_max = 265 nm), an excitation spectrum (λ_ex values = 357, 443, and 454 with monitoring at 533 nm), and an emission spectrum (λ_em = 536 nm with excitation at 430 and 450 nm) in methanol. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 659–674, 2002; DOI 10.1002/pola.10134     

Synthesis and studies of some 4-substituted phenyl-4'-azopyridine-containing hydrogen-bonded supramolecular mesogens

Novel azopyridine-containing supramolecular liquid crystalline (LC) materials built via 1 : 1-heterointermolecular hydrogen bonding between some 4-substituted phenyl-4'-azopyridines and 4- n -alkyloxybenzoic acids are reported. These hydrogen-bonded LC complexes exhibit well defined nematic, smectic A and smectic C phases over wide ranges of temperature depending upon the number of carbon atoms present in the alkyl chains. The formation of pure LC materials on 1 : 1-complexation could be confirmed from the phase diagrams of the binary mixtures, which clearly indicated a melting maximum for the 50 mol % mixture as well as the presence of two eutectic points on either side of this mixture.     

Fully aromatic thermotropic liquid crystalline polyesters of 3,4′-dihydroxybenzophenone

A series of fully aromatic, thermotropic polyesters, derived from 3,4′-dihydroxybenzophenone and various aromatic dicarboxylic acids, was prepared by the high-temperature solution polycondensation method and examined for thermotropic behavior by a variety of experimental techniques. The aromatic dicarboxylic acids used in this study were 2,6-naphthalenedicarboxylic acid, 4,4′-bibenzoic acid, and terephthalic acid. The two homopolymers of 3,4′-DHB with either 2,6-NDA or 4,4′-BBA formed nematic LC phases at 285°C and 255°C and also exhibited isotropization transitions (T_i) at 317°C and 339°C, respectively. The copolymer of 3,4′-DHB with 50% TA and 50% 2,6-NDA also formed a nematic LC phase and had a broader range of LC phase than that of its respective homopolymers. Two other copolymers of 3,4′-DHB, both containing 50% 4,4′-BBA, also formed nematic LC phases at low T_f values. All of the thermotropic polyesters had high thermal stabilities. © 1994 John Wiley & Sons, Inc.     

Asymmetric N-heterocyclic carbene benzimidazolium salts and their silver(I) complexes: potential as ionic liquid crystals

The synthesis and characterisation of a homologous series of monodentate benzimidazolium salts, 1–4 and their mononuclear silver(I)–NHC (where NHC = N-heterocyclic carbene) complexes, 5–8, are reported. The benzimidazolium salts were prepared from the N-alkylation of 1-methyl-benzimidazole with alkyl halides of varying carbon chain lengths. The mono silver(I)-NHC complexes, 5–8, were prepared by the reaction of the benzimidazolium salts with Ag₂O. All the synthesised compounds were fully characterised by ¹H-nuclear magnetic resonance (¹H-NMR), ¹³C-NMR and fourier-transform infrared (FTIR) spectroscopy. The molecular structures of compounds 3·PF₆, 4·PF₆, 7 and 8 were elucidated through single-crystal X-ray diffraction analyses. We postulate that the attachment of long alkyl chains to the heterocyclic core of 1-methyl benzimidazole could induce mesophase formation. The liquid crystalline behaviour of the benzimidazolium salts was investigated by polarised optical microscope and differential scanning calorimetry. Salts 3 and 4 were found to be thermotropic liquid crystals which exhibited a smectic A phase. However, upon complexation with silver(I) ions, all the Ag(I)–NHC complexes are found to be non-mesogenic.     

Preparation and thermotropic liquid crystalline properties of semirigid copolyurethanes composed of biphenyl units and partially fluorinated aliphatic chains

New semirigid thermotropic liquid crystalline (LC) copolyurethanes 4 and 5 made up of biphenyl units and partially fluorinated aliphatic chains in the backbones were synthesized by melt polycondensation of a mixture of a dioxydihexanol of biphenyl 1 and two fluorine-containing diols 2a , b taken in definite feed mole ratios with alkylene diphenyl dicarbamates 3a–i having various lengths of aliphatic chains. The assigned structures of copolyurethanes 4 and 5 were identified by FTIR, ¹H- and ¹³C-NMR spectra, and elemental analyses. The thermal and mesogenic properties were evaluated by differential scanning calorimetry (DSC), thermal mechanical analyses (TMA), polarizing microscopy, and temperature-changeable X-ray analyses, whose measurements indicated that the copolymers 4 and 5 form thermotropic nematic phases and have glass transition steps around room temperature. It is suggested that the incorporation of partially fluorinated aliphatic chains into the backbones has no drastic effect on the LC formation in the semirigid copolyurethanes 4 and 5 . © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1243–1249, 1998